Polytriazapentadiene polymers

ABSTRACT

This invention relates to triazapentadiene polymers having at least one triazapentadiene unit of the formula: WHEREIN EACH X is selected from chlorine and fluorine, each Y is selected from halogen and perhalo lower alkyl, m and n are positive integers greater than zero, x is from 3 to 1 million, (CXY)mZ(CXY)n- is a divalent polyhalo organic radical where the sum of m plus n plus the number of equivalent units in Z is at least 4 and Z is at least one member of the group of perhalo lower alkylene, perhalo lower alkylidene, omega-hydroperhalo lower alkylidene, keto, oxy, thio, sulfoxide, sulfone, WHEREIN R is selected from perhalo lower alkyl and omegahydroperhalo lower alkyl, polyperfluorooxyalkylene where each alkylene unit has from two to ten carbon atoms and the units are from 2 to 35 in number, poly(perfluoroalkylene dioxy) where each alkylene unit has from two to ten carbon atoms and the units are from 2 to 35 in number, perfluoroalkylene dioxy, perhalo lower alkylamino, perhalocyclopentylene, perhalocyclohexylene, perhalopyridinediyl, perhalopyrazolidinediyl, perhalopyranylene, perhalopiperidylene, perhalophenylene, perhalonaphthalenediyl, perhalodicalinylene, oxadiazolylene, triazolylene, triazinylene, and aryl perhalo lower alkylene wherein substituents on the said aryl group are selected from hydrogen, lower alkenyl, chloro, fluoro, lower alkoxy, nitro, nitroso, cyano, and alkoxy carbonyl; and terminal groups individually selected from the group consisting of nitrile, amidine, -(CXY)mZ(CXY)nCN, alkyl imidates, thioalkyl esters, thioaryl esters, thiolalkyl esters, thiolaromatic esters, alkyl, omega-hydroperhaloalkyl, perhaloalkyl, perhaloalkene, perhaloalkyne, aryl, lower alkyl ester, aryl ester, carbourea, and perhalo lower alkyl amidine.

United States Patent Dorfman et al.

1451 *June 13, 1972 [54] POLYTRIAZAPENTADIENE POLYMERS [73] Assignee:Hooker Chemical Corporation, Niagara Falls, NY.

The portion of the term of this patent subsequent to Jan. 13, 1987, hasbeen disclaimed.

22 Filed: Sept. 23, 1969 21 Appl. No.: 860,413

[ Notice:

Related U.S. Application Data [63] Continuation-impart of Ser. No,533,418, March 11,

1966, Pat. No. 3,489,727.

3,369,002 2/1968 Griffin ..260/78.4

Primary Examiner.loseph L. Schofer Assistant ExanzinerJohn Kight, lll

AnorneyPeter F. Casella, Donald C. Studley, Richard P.

Mueller, James F. Mudd and Edward A. Meilman [5 7] ABSTRACT Thisinvention relates to triazapentadiene polymers having at least onetriazapentadiene unit of the formula:

NH NH:

wherein each X is selected from chlorine and fluorine, each Y isselected from halogen and perhalo lower alkyl, m and n are positiveintegers greater than zero, x is from 3 to 1 million, -(CXY),,.Z(CXY),,is a divalent polyhalo organic radical where the sum of m plus n plusthe number of equivalent units in Z is at least 4 and Z is at least onemember of the group of perhalo lower alkylene, perhalo lower alkylidene,omegahydroperhalo lower alkylidenejlceto, 0Xy, thio, sulfoxid;e,

sulfone, RN O wherein R is selected from perhalo lower alkyl andomegahydroperhalo lower alkyl, polyperfluorooxyalkylene where eachalkylene unit has from two to ten carbon atoms and the units are from 2to 35 in number, po1y(perfluoroal kylene dioxy) where each alkylene unithas from two to ten carbon atoms and the units are from 2 to 35 innumber, perfluoroalkylene dioxy, perhalo lower alkylamino,perhalocyclopentylene, perhalocyclohexylene, perhalopyridinediyl,perhalopyrazolidinediyl, perhalopyranylene, perhalopiperidylene,perhalophenylene, perhalonaphthalenediyl, perhalodicalinylene,oxadiazolylene, triazolylene, triazinylene, and aryl perhalo loweralkylene wherein substituents on the said aryl group are selected fromhydrogen, lower alkenyl, chloro, fluoro, lower alkoxy, nitro, nitroso,cyano, and alkoxy carbonyl; and terminal groups individually selectedfrom the group consisting of nitrile, amidine, -(C- XY),,,Z(CXY),,CN,alkyl imidates, thioalkyl esters, thioaryl esters, thiolalk l estersthiolaromatic esters, alkyl, omegahydroperhaloal yl, perhaloalkyl,perhaloalkene, perhaloalkyne, aryl, lower alkyl ester, aryl ester,carbourea, and perhalo lower alkyl amidine.

18 Claims, No Drawings POLYTRIAZAPENTADIENE POLYMERS REFERENCE TO PRIORAPPLICATION wherein the Xs are halogens selected from chlorine andfluorine, and the Ys are selected from halogen and perhalo lower alkyl;m and n are positive integers greater than zero; x is from 1 to 1million; (CXY),,,Z(CXY),,- is a divalent polyhalo organic radical wherethe sum of m plus n plus the number of equivalent units in Z is at leastfour, and Z is a difunctional group defined below.

An object of this invention is to provide new halogenated polymerscontaining triazapentadiene groups in the polymeric chain.

It is another object of this invention to provide a process for theproduction of liquid low molecular weight polymers.

It is another object of this invention to provide a process for theproduction of solid polymers in contrast to liquid, lowmolecular weightpolymers.

Another object of this invention is to provide high molecular weightlinear or essentially linear polymers which are soluble in organicsolvents and which can be converted to linear or essentially linearsoluble triazine polymers.

Another object is to provide new and useful solutions of high molecularweight polymersv Various other objects and advantages of the presentinvention will become apparent to those skilled in the art from theaccompanying description and disclosure.

According to the present invention the polytriazapentadiene polymer isformed by an addition type of reaction between halogen-containingorganic dinitrile compounds and ammonia and/or diamidine compounds. Thisis illustrated by the following equations:

where x is a positive integer from one to one million.

(x)NC(CF2)4CN NH wherein x is an integer from 1 to 1 million.

The haloalkylene groups, illustrated in equations (1) and (2) byperfluorobutylene groups in both the dinitrile and the diamidinestarting materials, respectively, to be used in this invention, includealkylene groups having at least 4 carbon atoms in which the carbon atomsalpha (or) to the nitrile or amidine radical is perhalogenated and thecarbon atom beta to the nitrile or amidine radical is at least partiallyhalogenated. The halogens are selected from the group consisting offluorine, chlorine and mixtures thereof. Perfluoroalkylene groups arepreferred, that is, an alkylene radical wherein all the hydrogen atomshave been replaced by fluorine atoms. In addition to perhaloalkylenegroups, in-

cluded within the scope of this invention are difunctional polyhaloorganic radicals defined by the formula: (CX- Y),,,Z(CXY),,-, whereinthe Xs in any (CXY) group are halogens, the Ys in any (CXY) group areselected from halogen and perhalo lower alkyl, m and n are positiveintegers greater than zero, and the sum of m plus n plus the number ofequivalent units in Z is at least 4, and Z is selected from perhalolower alkylene, perhalo lower alkylidene, omegahydroperhalo loweralkylidene, keto, oxy, thio, sulfoxide, sulfone,polyperfluorooxyalkylene where each alkylene unit has from two to 10carbon atoms and the units are from 2 to 35 in number,poly(perfluoroalkylenedioxy) where each alkylene unit has from two to 10carbon atoms and the units are from 2 to 35 in number,perfluoroalkylenedioxy, perhalo lower alkylamino, perhalocyclopentylene,perhalocyclohexylene, perhalopyridenediyl, perhalopyrazolidinediyl,perhalopyranylene, perhalopiperidylene, perhalophenylene,perhalonaphthalenediyl, perhalodecalinylene, oxadiazolylene,triazolylene, triazinylene and aryl perhalo lower alkylene whereinsubstituents on the said aryl group are selected from hydrogen, loweralkenyl, chloro, fluoro, lower alkoxy, nitro, nitroso, cyano, and alkoxycarbonyl. The halogens represented by the Xs and Ys can be the same ordifferent halogens selected from the group consisting of chlorine,fluorine, and mixtures thereof. The above lower alkyl" groups have fromone to 10 carbon atoms in them. The abovedefined divalent polyhaloorganic radical in the dinitrile starting material can be the same as,or different from, the abovedefined divalent polyhalo organic radical inthe diamidine starting material. Throughout this disclosure whereverhalogen" is referred to, it is intended to be those halogens selectedfrom the group consisting of chlorine and fluorine.

Among the alkylene groups included within the scope of this inventionare perfluoro lower alkylene, such as perfluorobutylene,perfluoropentamethylene and perfluorohexamethylene, branched chainalkylene groups, such as perfluoroethylbutylene,perfluoromethylhexamethylene, perfluorobutyldodecamethylene,phenylperfluorohexamethylene, substituted phenylperfluorohexamethylenewhere the substituents are selected from the chloro-, fluoro-, nitro-,nitroso-, nitrile, alkoxy, carbalkoxy, vinyl and styryl. A preferredalkylene group is perfluoro lower alkyl tetramethylene group, especiallythe perfluoroethyltetramethylene group. The alkylene chain length can befrom four to 45 carbon atoms in length, with four to 22 carbon atomsbeing an intermediate preferred length, while chains of from four to 10carbon atoms are the most preferred.

Another preferred divalent polyhalo organic radical is apolyperfluorooxyalkylene where each alkylene unit has from two to 10carbon atoms and the units are from 2 to 35 in number.

The term triazapentadiene, as used throughout the specification andclaims, refers to a divalent radical of the formula:

Conveniently, a perhaloalkylene dinitrile in a solvent is stirred, andfinely divided perhaloalkylene diamidine is added to it continuously orintermittently as the reaction proceeds, until the desired degree ofpolymerization is obtained. The molecular weight can be controlled togive a polymer of at least 3 monomer units. Thus, it can be controlledto give a polymer of 3, 5, 10, or 3,000 monomer units. Still highermolecular weight polymers can also be obtained. Preferably, the numberof monomer units is about 4 to about 3,000 units.

It is preferred to use pure or substantially pure starting materials inorder to reduce the amount of chain termination.

The triazapentadiene polymers formed by reaction of these dinitrileswith ammonia and/or diamidines will normally be terminated by nitrile oramidine groups. The presence of impurities in either the dinitrile,diamidine, diluent or equipment or the special nature of themanufacturing process causes the terminal groups on the triazapentadienepolymer to have other groups which may not participate in apolymerization reaction with a nitrile group or ammonia, or an amidinegroup. Thus, if the dinitrile contains perhaloalkyl nitrile, oromegahydroperhaloalkylnitrile, the polymers are terminated, to someextent at least, with perhalo-alkyl or omega-hydroperhaloalkyl groups.If the dinitrile contains ester or amide functions, then terminal groupsinclude the corresponding ester or amide groups respectively.

Other terminal groups are embraced, such as, alkyl imidates, thioalkylesters, thioaryl esters, thiolalkyl esters, thiolaromatic esters, alkylgroups, omega-hydroperfluoroalkyl groups, perhaloalkyl groups,perhaloalkene groups, perhaloalkyne groups, aryl groups such as phenyl,tolyl, nitrophenyl, chlorophenyl, methoxyphenyl, acetaminophenyl, anddimethylaminophenyl, lower alkyl ester groups, aryl ester groups,carbourea i h (CN HCN H groups, and perhalo lower alkyl amidine groupswhere R is selected from perhalo lower alkyl and omegahydroperfluorolower alkyl. These end groups would normally be derived to a substantialextent from the starting materials, including the impurities present.

Polymer branching can be introduced at the triazapentadiene group by thepresence of of an acylating compound which also contains a nitrilegroup. Thus, chlorocarbonylperhaloalkyl cyanides, which may be presentin the dinitrile being used would acylate a triazapentadiene group, andcause growth of a polymer branch from the pendant nitrile group.

Other compounds which cause branching are nitrile carboxylic anhydrides,nitrile-dinitrophenyl esters, nitrile-sulfonic anhydrides,nitrile-phosphoric anhydrides, nitrile-carboxylic acid bromides,fluorides, and iodides, nitrile isocyanates, nitrile-carbodiimides, andthe like. Very active dinitriles, such as perfluorornalononitrile,perfluorosuccinonitrile, and perfluoroglutaronitrile, could also reactat a triazapentadiene group and initiate chain-branching.

It has been discovered that polymeric chains having nitrile terminalgroups react with other polymeric chains having amidine terminal groupsto give polymeric chains of higher molecular weight. it has also beendiscovered that the perhaloalkylene radical of the nitriles or amidinesused need not be alike in all reacting species. Thus, for example, one.particular perfluoroalkylene dinitrile may be reacted with a diamidineprepared from a different perfluoroalkylene dinitrile to give acopolymer. The process can also be efi'ected with yet a third dinitrileor diamidine having yet a different type of perfluoroalkylene group togive a terpolymer, and so on, providing the proper dinitrile-diamidinestoichiometry is maintained.

In addition, low molecular weight polymers containing one kind ofperhaloalkylene radical in the chain can be reacted with other lowmolecular weight polymers containing a different type of perhaloalkyleneradical in the chain to give block polymers which are different fromthose described above.

Polymers in which the difunctional polyhalo organic triazapentadieneradicals are distributed in random order are obtained by reaction ofmixtures of dinitriles with a diamidine or a mixture of diamidine in amolar ratio approaching 1:].

A similar polymer is obtained by treating reaction of a mixture ofdinitriles with ammonia in a molar ratio approaching lzl. Co-monomers inaddition to the above defined dinitriles may be used with the abovedefined dinitriles and diamidines.

Thus, a number of different polymers can be prepared in which the typeof perhaloalkylene radicals can be connected in the chains in repeating,alternating, or in random order, or in blocks of like radicals,depending on the nature of the reacting species and the order in whichthey are permitted to react and, again, providing the properdinitrile-diamidine and/or dinitrile ammonia stoichiometry bemaintained.

The dinitriles employed in this invention are perfluoroadiponitrile,perfluorosuberonitrile, and perfiuorosebaconitrile. Other dinitriles mayalso be used where the perhaloalkylene group numbers from four to 45 perhalomethylene units. The higher homologous dinitriles or theirprecursors can be prepared from intermediates which, in turn, can beprepared by known telomerization reaction procedures. The various longerchain materials are desirable because they permit the synthesis of blockpolymers having desirable properties in the ultimate triazine polymerover a wide temperature range. Such dinitriles includeperfluoroadiponitrile, perfluorosuberonitrile, perfluoropimelonitrile,pertluoroazelanitrile, perfluorosebaconitrile,perfluorododecanedinitrile, perfluorooctadecanedinitrile,perfluorotetracosanedinitrile, perfluorotriacontanedinitrile,perfluorotetracontanedinitrile, and the like.

Since maintenance of desirable properties over a wide range oftemperatures in the end-product triazine polymer is desired, the use ofoxa-perfluoroalkylenedinitriles and branched perfluoroalkylenedinitrileswhich are otherwise very similar to perfluoroalkylenedinitriles aredesirable for the polymer synthesis. Such dinitriles include 3oxa-perfluorosebaconitrile 5,9-dioxa-perfluorotetradecanedinitrile,oxa-perfluoropimelonitrile oxaperfluoroadiponitrile,tetraoxaperfluorotetracosanedinitrile, andpentaoxa-perfluorotriacontanedinitrile.

Branched periluoroalkylenedinitriles, including perfluoro-3-ethyladiponitrile, perfluoro-2-ethyladiponitrile, perfluoro-3-propyladiponitrile, perfluoro-3-methylpimelonitrile,perfluoro-4-ethylpimelonitrile, perfluoro-3-methylsuberonitrile,

perfluoro-4-propylsuberonitrile, perfluoro-4- methylazelaonitrile, periluoro-S-butylsebaconitrile, 2 l 0- bis( trifluoromethyl )-3,9-dioxaundecanedinitrile, 2, 1 l

bis( trifluoromethyl )-3, l O-dioxadodecanedinitrile, per-fluoro-2-ethyl-3-methyladiponitrile, perfluoro-3,5-dimethylsuberonitrile,perfluoro-3,o-diethylsebaconitrile and perfluoro- 3 ,6-diethyl-9, l3-dimethyloctadecanedioicnitrile are embraced within the startingmaterials of this invention.

The diamidines employed in this invention are those derived from theabove dinitriles and the like. The diamidines are derived from thereaction of the corresponding dinitrile with ammonia, boiling out theexcess ammonia, leaving the diamidine behind.

Among the specific triazapentadiene compounds or polymers embracedwithin the scope of this invention are: bis( 4-cyanoperfluorobutyl)triazapentadiene bis( 8-cyanoperfluorooctyl)triazapentadiene, bis(S-cyano-oxa-perfluoroamyl )triazapentadiene,poly(perfluorohexamethylenetriazapentadiene,) poly(perfluorotetramethylenetriazapentadienepoly(perfluoropentamethylenetriazapentadiene poly(perfluorohexamethylenetriazapentadiene poly(perfluoroheptamethylenetriazapentadiene poly(perflurooctamethylenetriazapentadiene poly(perfluorodecamethylenetriazapentadiene poly( perfluoroundecamethylenetriazapentadiene poly(perfluorododecamethylenetriazapentadiene poly(perfluorotn'decamethylenetri azapentadiene poly(perfluorotetradecamethylenetriazapentadiene poly(perfluorotetramethyleneperfluorohexamethylenetriazapentadiene), poly(periluorotetramethyleneperfluorooctamethylenetriazapentadiene The blockterpolym er: poly(perfluorohexamethyleneperfluorododecamethyleneperfluorooctadecamethyleneperfluorotetracosmethylene)tr iazapentadiene, poly( dioxa-perfluorooctamethylene)tn'azapentadiene, and poly(oxa-perfluoropentamethyleneperfluorotetradecamethylene)triaza-pentadiene.

It has been found these dinitriles react to form diamidines when treatedwith ammonia. To some extent perfluoroadiponitrile forms the cycloperfluoroadiprimidine when treated with ammonia, but since this reactswith perfluoroalkyl nitriles more slowly than diamidines, and since itcan be removed from perfluoroadipamidine, linear polymers can be madefrom it by the processes of this invention. Perfluoroglutaronitrile,perfluorosuccinonitrile and difluoromalononitrile do not give stablediamidines when treated with ammonia, and therefore have limited use insynthesizing linear polymers.

The polymerization process of this invention may be carried out betweenabout minus 80 and 120 C., but is conveniently carried out at ambienttemperature, i.e., room temperature. Since heat is evolved by thereaction, cooling is desirable to avoid the possibility of vaporizationof the dinitrile and reaction occurring out of the liquid reaction zone.At temperatures above about 120 C., the diamidine tends to becomeunstable and decomposes. At temperatures below minus 80 C., the reactionmay become sluggish. The preferred temperature range is between minus 30and 70 C The reaction is controlled more easily if carried out in thepresence of a diluent, inert under the conditions of reaction, but nodiluent is necessary. Suitable diluents are 1,2- dimethoxyethane,diethylether, acetonitrile, and tetrahydrofuran. Of these1,2-dimethoxyethane is the preferred solvent for high molecular weightperfluoroalkylenetriazapentadiene polymers. Other solvents may be used,such as dioxane, diethylcarbitol, anisole, chloroanisole,dimethoxymethane, dimethylsulfoxide, tert.-butano1, non-halogenatednitriles as a class, such as benzonitrile, succinonitrile,glutaronitrile, and acetonitrile; perhalogenated aliphatic solvents suchas perfluorokerosene, tetrachloroethylene, methylene chloridetrichlorotrifluoroethane, perfluorotributylaminedifluorotetrachloroethane, fluorotrichloromethane, perfluoropyranes,perfluorotetrahydrofurans, and dibromotetrafluoroethane; certain estersolvents such as methylbenzoate, ethyl acetate, and propyl acetate; aswell as other diluent solvent means such as dimethylacetamide tertiaryamyl alcohol, isopropanol, nitromethane, hexafluoroxylene,benzotrifluoride, chlorobenzene, dichlorobenzene, benzene, toluene,xylene, hexane, heptane, octanes, mineral spirits, apinene, turpentine,and the like.

It is often advantageous to add finely divided diamidine compound as asolid or a slurry in an inert liquid to a concentrated solution ormixture of a dinitrile compound in reaction liquid. As the polymerincreases in molecular weight and the solution becomes more viscous,additional inert liquid may be added until the desired viscosity andpolymer molecular weight is obtained. The progress of the polymerizationcan be followed by measuring the viscosity and the amount of liquidused. It is preferable to use concentrated solutions since a largerproportion of low molecular weight macrocyclic compounds can be formedin a dilute reaction medium due to intramolecular reaction.

As another special form of the invention, the reaction can be controlledto give a monotriazapentadiene compound, il-

lustrated by the formula:

NH NHz NH NHz where the divalent group -(CXY,,,Z(CXY),, is as definedabove.

They are prepared by addition of ammonia to excess dinitrile, removingthe unreacted dinitrile, to leave the monotriazapentadienedinitrile.These compounds give fluid bis(cyanoperhaloalkylene) triazines which areuseful as such, and which may also be used as intermediates for theproduction of other polymers.

The reaction can also be carried out by adding ammonia to theconcentrated solution or mixture of the dinitrile compound and inertliquid, instead of adding a diamidine. Dilution may be effected as themolecular weight increases. This technique is especially advantageousfor making low molecular weight polymers.

Furthermore, the reaction can be carried out by adding the dinitrile inslight excess to a mixture of solid diamidine and inert liquid such asdimethoxyethane. When the low molecular weight polymer formation iscomplete, further polymerization is carried out by carefully controlledaddition of ammonia to the polymer solution until a high molecularweight polymer is obtained.

Another polymerization method may be employed where the diamidine isprepared in situ with dinitrile, solvent, and ammonia with thepolymerization vessel. The polymerization process may then be effectedby the addition of dinitrile to the diamidine and liquid diluent until ahigh molecular weight polymer is obtained. The polymerization may alsobe effected by adding dinitrile in slight excess to the diamidine andhigher polymer made by the further addition of small amounts of ammonia.

The novel polymers of the present invention are not thermally stable assuch above about 120 C., but when treated as described in copendingapplication Ser. No. 533,430, filed Mar. 1 l, 1966, they are convertedto soluble, thermally stable poly(perhaloalkylenetriazine) polymers,useful as gaskets, seals, sealants, O-rings, bladders, tires, hoses,greases, lubricants, hydraulic fluids, wire insulation and the like.

The following examples will further illustrate the nature of the presentinvention; however, the invention is not intended to be limited to theseexamples. Parts are by weight and tem' peratures in degrees Centigradeunless otherwise indicated.

EXAMPLE 1 Preparation of Poly(perfluorotetramethylenetriazapentadiene)followed by conversion toPoly(perfluorotetramethyleneperfluoropropyltriazine) Toperfluoroadipamidine, 0.429 grams, in a 50 milliliter round-bottomedflask containing a magnetic stirrer, was added perfluoroadiponitrile,0.397 grams, and acetonitrile, 5.5 milliliters. The mixture was stirredand allowed to warm to ambient temperature, 25 C. In 2 hours the mixturewas homogeneous. The solution was concentrated to a residue which wasdried under vacuum.

The perfluorotetramethylenetriazapentadiene polymer residue had areduced viscosity of 0.02 at 0.5 grams per deciliter in tetrahydrofuran.

Conversion to triazine polymer with perfluorobutyric anhydride gavepoly(perfluorotetramethyleneperfluoropropyltriazine) a viscous greasewith a characteristic triazine absorption band at 1,550 cm.

EXAMPLE 2 Preparation of Po1y(perfluorohexamethylenetriazapentadiene)and conversion to Poly(perfluorohexamethyleneperfluoropropyltriazine) Toperfluorosuberamidine, 1 1.248 grams, and tetrahydrofuran, 30milliliters, in a milliliter round-bottomed flask at 0 C. was addedperfluorosuberonitrile, 10.25 grams, in 75 minutes. The mixture wasallowed to warm to room temperature and was stirred for 5 days. A samplewas dried under vacuum, and the perfluorohexamethylenetriazapentadienepolymer obtained was found to have an intrinsic viscosity of 0.35deciliters per gram in tetrahydrofuran, and a molecular weight of37,000, and had the appearance of a white rubbery gum.

The polymer was converted by reaction with excess perfluorobutyricanhydride to the corresponding triazine polymer which had a molecularweight of 33,000 (about 100 monomer units).

EXAMPLE 3 Preparation of CopolymerPoly(pertluorohexamethyleneperfluorooctamethylenetriazapentadiene) To10.5 grams of perfluorosuberonitrile, in 10 milliliters ofdimethoxyethane, was added 6.72 grams of perfluorosebacamidine andperfluorosuberamidine (30:70 by weight mixture) in 48 hours withstirring in a nitrogen gas atmosphere at room temperature. Then 5milliliters of dimethoxyethane were added. In the next 48 hours, 2.39grams more of perfluorosuberamidine, were added, and 15 milliliters moredimethoxyethane. The temperature was then raised to 50 to 55 C. andperfluorosuberamidine and dimethoxyethane were added in portionsintermittently during 18 days until 11.55 grams of amidine and 95milliliters of dimethoxyethane had been added. The resultantperfluorohexamethyleneperfluorooctamethylenetriazapentadiene copolymerhad an intrinsic viscosity in dimethoxyethane of 1.0 deciliters pergram. The molecular weight, determined by membrane osmometry, was100,000 (about 300 monomer units).

EXAMPLE 4 Preparation of Po1y(perfluorohexamethylenetriazapentadiene) To23.5 grams of perfluorosuberonitrile and 17 milliliters of1,2-dimethoxyethane in the nitrogen atmosphere at C., ammonia was addedwith stirring. When 980 milliliters of ammonia had been consumed, 20milliliters more of 1,2- dimethoxyethane were added. When 1,100milliliters of ammonia had been consumed, 22 milliliters of1,2-dimethoxyethane were added. After 1,320 milliliters of ammonia hadbeen consumed, l0 milliliters more of 1,2-dimethoxyethane were added.When 1,374 milliliters of ammonia had been added, the reaction wasconsidered finished, for the solution was partially gelled. Therecovered perfluorohexamethylenetriazapentadiene polymer had anintrinsic viscosity of 0.355 deciliters per gram in 1,2dimethoxyethane.

A similar reaction gave a poly(perfluoroheih amethylenetriazapentadiene)product of intrinsic viscosity 0.13 deciliters per gram in1,2-dimethoxyethane. Conversion by the process of Example 1, gave atriazine polymer having an intrinsic viscosity of 0.51 deciliters pergram in hexafluoroxylene.

Using the method of Example 4 by substituting perfluorooxapimelonitrilefor perfluorosuberonitrile there can be obtained the correspondingpoly(perfluorooxapentam ethylenetriazapentadiene). By substitutingperfluoroethyladiponitrile for perfiuorosuberonitrile there can beobtained poly( periluoroethyletramethylenetriazapentadiene). Bysubstituting perfluorotetradecane dinitrile for perfluorosuberonitrilethere can be obtained poly(perfluorododecamethylenetriazapentadiene).

EXAMPLE Preparation of Po1y(perfluorohexamethylenetriazapentadiene)Perfluorosuberamidine, (1.9740 grams) having a melting point of 188 to190 C. in 6 milliliters of anhydrous tetrahydrofuran was stirredmagnetically in 50 milliliters round bottom flask in an ice bath. Tothis were added 1.747 grams of perfluorosuberonitrile in 1 minute, andthe solution was stirred in ice for 17 hours. Particles of amidine werestill observed, so additional nitrile was added until about 12 percentexcess over the theoretical amount was consumed. The amidine was thencompletely dissolved. A sample of the product was removed for analysis.A small band at 4.35 microns in the infrared spectrum of the reactionmixture sample was observed, indicating the presence of excess nitrilegroups. The unpurified amidine used may have had some free ammonia. Asample of the solution was dried under vacuum and gave a residue ofinelastic film. The solid triazapentadiene polymer had an intrinsicviscosity in tetrahydrofuran of 0.36 deciliters per gram. The numberaverage molecular weight in tetrahydrofuran by membrane osmometry was37,000 (about monomer units). Differential thermal analysis showedendotherms at C. and 186 C. identified as melting and decompositionrespectively in a melting point apparatus.

EXAMPLE 6 Preparation of Poly(perfluorooctamethylenetriazapentadiene) Around bottom flask was fitted with a gas inlet tube, a gas bubblecounter in the inlet line, and a magnetic stirrer. In it a solution ofperfluorosebaconitrile, 15 grams and 32 milliliters of tetrahydrofuranwas kept saturated with anhydrous ammonia for 2 hours. Condensationproducts of ammonia and the dinitrile were thereby formed asintermediates, which broke down in the presence of excess ammonia togive perfluorosebacamidine as a white solid which precipitated out, asperfluorosebacamidine. More perfluorosebaeonitrile, 15 grams, was thenadded until the solid perfluorosebacamidine was all consumed, asevidenced by its being dissolved. A sample was removed for analysis. Theinfrared absorption spectrum showed a nitrile peak at 4.35 microns.Ammonia was then added in small volumes until the nitrile absorptionpeak disappeared and the solution became viscous. A sample was driedunder vacuum, probably incompletely, to give a slightly tackytriazapentadiene polymer of intrinsic viscosity of 0.38 deciliters pergram. The differential thermal analysis (DTA) showed a continuousendotherm to the melting point of 147 C. In a sealed tube the samplestarted to wet the glass wall at 100 C. with complete fusion at 156 C.An endotherm at 189 C. was associated with a decomposition which wasobserved in a melting point tube.

EXAMPLE 7 Preparation ofPoly(perfluoropropylcyanoperiluoropropylperfluorohexamethylenetriazine)and vulcanization Thereof A poly(perfluorohexamethylenetriazapentadiene)polymer was prepared by the addition of perfluorosuberamidine toperfluorosuberonitrile in 1,2-dimethoxyethane. A polymer of intrinsicviscosity 0.9 deciliters per gram was obtained. The polymer, indimethoxyethane solution, 65 grams (13.7 percent by weight of polymer),was added from an additional funnel with stirring to a mixture ofperfluorobutyric anhydride, 72 grams, and 4-cyanoperfluorobutyrylchloride, 28 grams, in a closed round-bottomed flask, which was ventedoccasionally to release hydrogen chloride which was formed as abyproduct. The mixture was stirred 30 minutes, then the volatilematerials were removed by vacuum distillation to C. at 0.1 millimetersof mercury. A sample of the recovered triazine polymer, 2.5 grams(reduced viscosity, 0.25 at 0.3348 grams per deciliter), was milled withsilver oxide, 0.25 grams, and molded at 130 to 160 C. The moldedspecimen had a tensile strength of l,030 pounds per square inch at 75percent elongation and was vulcanized.

The 4-cyanoperfluorobutyryl chloride used in the above example isbelieved to be a new composition of matter, and separately claimed inSer. No. 573,195 filed Aug. 18, 1966.

EXAMPLE 8 Preparation ofPoly(perfluorotetramethyleneperfluorohexamethylenetriazapentadiene) Toperfluoroadiponitrile, 16.5 grams, and 1,2-dimethoxyethane, milliliters,was added perfluorosuberamidine, 26.3 grams.

The addition was made during 24 hours, and additional dimethoxyethane,45 milliliters, was added in portions during the reaction. The polymerhad an infrared absorption spectrum typical of the triazapentadienestructure.

EXAMPLE 9 Preparation ofPoly(perfluorotetramethyleneperfluorohexamethylenetn'azine) Thetriazapentadiene polymer of Example 8, 25 grams in dimethyoxyethane, wasadded with stirring to perfluorobutyric anhydride, 82 grams, in a periodof 2 hours at 25 to 30 C. The polymer was recovered by vacuumdistillation of the volatile material and vacuum drying of the residue.The polymer recovered had a reduced viscosity of 0.01 grams perdeciliter and had infrared absorption at 6.4 microns, characteristic ofthe triazine group.

As many widely different embodiments of this invention may be madewithout departing from the spirit and scope thereof, it is to beunderstood that this invention is not limited to the specificembodiments thereof.

We claim:

1. The triazapentadiene polymer consisting essentially of 3 to 1 milliontriazapentadiene units of the formula:

1TH ITH wherein each X is selected from chlorine and fluorine; each Y isselected from halogen and perhalo lower alkyl, m and n are positiveintegers greater than zero; (CXY),,,Z( CXY)" is a divalent polyhaloorganic radical having four to 45 carbon atoms and Z is at least onemember of the group of perhalo lower alkylene, perhalo lower alkylidene,omega-hydroperhalo lower alkylidene, keto, oxy, thio, sulfoxide,sulfone,

wherein R is selected from perhalo lower alkyl and omegahydroperhalolower alkyl, polyperfluorooxyalkylene where each alkylene unit has fromtwo to carbon atoms, poly( perfluoroalkylene dioxy) where each alkyleneunit has from two to 10 carbon atoms, perfluoroalkylene dioxy, perhalolower alkylamino, perhalocyclopentylene, perhalocyclohexylene,perhalopyridinediyl, perhalopyrazolidinediyl, perhalopyranylene,perhalopiperidylene, perhalophenylene, perhalonaphthalenediyl,perhalodecalinylene, oxadiazolylene, triazolylene, triazinylene and arylperhalo lower alkylene wherein substituents on the said aryl group areselected from hydrogen, lower alkenyl, chloro, fluoro, lower alkoxy,nitro, nitroso, cyano, and alkoxy carbonyl; and terminal groupsindividually selected from the groups consisting of nitrile, amidine,(CXY),,,Z(CXY),.CN, alkyl imidates, thioalkyl esters, thioaryl esters,thiolalkyl esters, thiolaromatic esters, alkyl,omega-hydroperfluoroalkyl, perhaloalkyl, perhaloalkene, perhaloalkyne,aryl, lower alkyl ester, aryl ester, carbourea, and perhalo lower alkylamidine.

2. The triazapentadiene polymer of claim 1 wherein the (CXY),,,Z(CXY)radical is a perfluoroalkylene group of (CXY),,,Z(CXY) radical is aperfluorooctamethylene group.

7. The triazapentadiene polymer of claim 2 wherein the (CXY),,,Z(CXY)radical is a perfluorododecamethylene group.

8. The triazapentadiene polymer of claim 2 wherein the (CXY),,,Z(CXY)radical is a perfluoro lower alkyl tetramethylene group where the saidperfluoro lower alkyl group has from one to ten carbon atoms.

9. The triazapentadiene polymer of claim 8 wherein the(CXY),,,Z(CXY),,,- radical is a perfluoroethyltetramethylene group.

10. The triazapentadiene polymer of Claim 1 wherein the (CXY),,,Z(CXY)radicals are perfluoroalkylene groups having four to 45 carbon atomsconnected by triazapentadiene groups in repeating, alternating or randomorder.

11. The triazapentadiene polymer of claim 10 wherein theperfluoroalkylene groups are perfluorohexamethylene andperfluorooctamethylene.

12. The triazapentadiene polymer of claim 10 wherein theperfluoroalkylene groups are perfluorotetramethylene andperfluorohexamethylene.

13. The triazapentadiene polymer of claim 10 wherein theperfluoroalkylene groups are perfluorotetramethylene andperfluorooctamethylene.

14. The triazapentadiene polymer consisting essentially of 3 to 1million triazapentadiene units of the formula T 1TH wherein each X isselected from chlorine and fluorine, each Y is selected from halogen andperhalo lower alkyl, m and n are positive integers greater than zero,and --(CXY),,,Z(CXY is a polyperfluorooxyalkylene radical where eachalkylene unit has from two to 10 carbon atoms and the units are from 2to 3 5 in number.

15. A block polymer in which at least one of the polymeric recurringunits is the triazapentadiene polymer of the formula defined in claim 1.

16. The block copolymer of claim 15 wherein the recurring units contain(CXY),,,Z(CXY),, radicals of perfluorotetramethylene andperfluorooctamethylene groups.

17. The triazapentadiene polymer consisting essentially of 3 5 to 1million triazapentadiene units of the formula:

wherein each X and Y is fluorine, Z is oxygen, m and n are positiveintegers greater than zero, and (CXY),,,Z(CXY),, has four to 45 carbonatoms.

18. The triazapentadiene polymer of claim 17 in which m plus n is 4.

2. The triazapentadiene polymer of claim 1 wherein the -(CXY)mZ(CXY)n-radical is a perfluoroalkylene group of four to 45 atoms.
 3. Thetriazapentadiene polymer of claim 2 wherein the -(CXY)mZ(CXY)n- radicalis a perfluoroalkylene group of four to 22 carbon atoms.
 4. Thetriazapentadiene polymer of claim 2 wherein the -(CXY)mZ(CXY)n- radicalis a perfluorotetramethylene group.
 5. The triazapentadiene polymer ofclaim 2 wherein the -(CXY)mZ(CXY)n- radical is a perfluorohexamethylenegroup.
 6. The triazapentadiene polymer of claim 2 wherein the-(CXY)mZ(CXY)n- radical is a perfluorooctamethylene group.
 7. Thetriazapentadiene polymer of claim 2 wherein the -(CXY)mZ(CXY)n- radicalis a perfluorododecamethylene group.
 8. The triazapentadiene polymer ofclaim 2 wherein the -(CXY)mZ(CXY)n- radical is a perfluoro lower alkyltetramethylene group where the said perfluoro lower alkyl group has fromone to ten carbon atoms.
 9. The triazapentadiene polymer of claim 8wherein the -(CXY)mZ(CXY)n- radical is a perfluoroethyltetramethylenegroup.
 10. The triazapentadiene polymer of Claim 1 wherein the-(CXY)mZ(CXY)n- radicals are perfluoroalkylene groups having four to 45carbon atoms connected by triazapentadiene groups in repeating,alternating or random order.
 11. The triazapentadiene polymer of claim10 wherein the perfluoroalkylene groups are perfluorohexamethylene andperfluorooctamethylene.
 12. The triazapentadiene polymer of claim 10wherein the perfluoroalkylene groups are perfluorotetramethylene andperfluorohexamethylene.
 13. The triazapentadiene polymer of claim 10wherein the perfluoroalkylene groups are perfluorotetramethylene andperfluorooctamethylene.
 14. The triazapentadiene polymer consistingessentially of 3 to 1 million triazapentadiene units of the formulawherein each X is selected from chlorine and fluorine, each Y isselected from halogen and perhalo lower alkyl, m and n are positiveintegers greater than zero, and -(CXY)mZ(CXY)n is apolyperfluorooxyalkylene radical where each alkylene unit has from twoto 10 carbon atoms and the units are from 2 to 35 in number.
 15. A blockpolymer in which at least one of the polymeric recurring units is thetriazapentadiene polymer of the formula defined in claim
 1. 16. Theblock copolymer of claim 15 wherein the recurring units contain-(CXY)mZ(CXY)n- radicals of perfluorotetramethylene andperfluorooctamethylene groups.
 17. The triazapentadiene polymerconsisting essentially of 3 to 1 million triazapentadiene units of theformula: wherein each X and Y is fluorine, Z is oxygen, m and n arepositive integers greater than zero, and -(CXY)mZ(CXY)n- has four to 45carbon atoms.
 18. The triazapentadiene polymer of claim 17 in which mplus n is 4.